The development in the field of coordination polymers or metal-organic coordination networks, MOCNs (metal-organic frameworks, MOFs) is assessed in terms of property investigations in the areas of catalysis, chirality, conductivity, luminescence, magnetism, spin-transition (spin-crossover), non-linear optics (NLO) and porosity or zeolitic behavior upon which potential applications could be based.

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Engineering coordination polymers towards applications

Instability of most prototypical metal organic frameworks (MOFs) in the presence of moisture is always a limita- tion for industrial scale development. In this work, we examine the dissociation mechanism of microporous paddle wheel frameworks M(bdc)(ted)0.5 [M=Cu, Zn, Ni, Co; bdc= 1,4-benzenedicarboxylate; ted= triethylenediamine] in controlled humidity environments. Combined in-situ IR spectroscopy, Raman, and Powder x-ray diffraction measurements show that the stability and modification of isostructual M(bdc)(ted)0.5 compounds upon exposure to water vapor critically depend on the central metal ion. A hydrolysis reaction of water molecules with Cu-O-C is observed in the case of Cu(bdc)(ted)0.5. Displacement reactions of ted linkers by water molecules are identified with Zn(bdc)(ted)0.5 and Co(bdc)(ted)0.5. In contrast,. Ni(bdc)(ted)0.5 is less suscept- ible to reaction with water vapors than the other three compounds. In addition, the condensation of water vapors into the framework is necessary to initiate the dissociation reaction. These findings, supported by supported by first principles theoretical van der Waals density functional (vdW-DF) calculations of overall reaction enthalpies, provide the necessary information for de- termining operation conditions of this class of MOFs with paddle wheel secondary building units and guidance for developing more robust units.

Stability and Hydrolyzation of Metal Organic Frameworks with Paddle-Wheel SBUs upon Hydration

Organometallic- and organic-based materials exhibiting the technologically important property of bulk magnetism have been designed, prepared, and studied. These magnets are prepared via conventional organic chemistry methodologies and unlike conventional inorganic-based magnets do not require metallurgical processing. Furthermore, these magnets are frequently soluble in conventional solvents, and examples have saturation magnetizations exceeding that of iron metal on an Fe or mole basis. Also, magnets with critical temperatures exceeding room temperature, magnets with coercive fields exceeding that of Co5Sm, and thin-film magnets have been prepared. This article highlights the collective joint research executed in our, as well as Arthur J. Epstein's, laboratories.

Organometallic- and organic-based magnets: New chemistry and new materials for the new millennium

In this paper, we report on a high-throughput (gram quantities) solvothermal method for the synthesis of copper terephthalate metal–organic frameworks in dmf. While the structure of MOF-2 and some of the associated polymorphs are well known, we know of no equivalent structural studies for the isostructural copper terephthalate (Cu–tpa). The material we have made crystallizes in the C2/m space group. Cu–tpa also exhibits reversible solvent-exchange properties. These properties make this material useful for potential applications in gas storage and catalysis applications. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Synthesis and Structure Characterization of Copper Terephthalate Metal–Organic Frameworks

Instability of most prototypical metal organic frameworks (MOFs) in the presence of moisture is always a limitation for industrial scale development. In this work, we examine the dissociation mechanism of microporous paddle wheel frameworks M(bdc)(ted)0.5 [M = Cu, Zn, Ni, Co; bdc = 1,4-benzenedicarboxylate; ted = triethylenediamine] in controlled humidity environments. Combined in situ IR spectroscopy, Raman, and Powder X-ray diffraction measurements show that the stability and modification of isostructual M(bdc)(ted)0.5 compounds upon exposure to water vapor critically depend on the central metal ion. A hydrolysis reaction of water molecules with Cu–O–C is observed in the case of Cu(bdc)(ted)0.5. Displacement reactions of ted linkers by water molecules are identified with Zn(bdc)(ted)0.5 and Co(bdc)(ted)0.5. In contrast,. Ni(bdc)(ted)0.5 is less susceptible to reaction with water vapors than the other three compounds. In addition, the condensation of water vapors into the framework is necessary to initia...

The reaction between CuCl2·2H2O and disodium terephthalate, Na2tp, in aqueous solution simultaneously produces chain, bis(aqua)[μ-(terephthalato-κO:κO‘)]copper(II), monohydrate, Cutp(OH2)2·H2O (1), and layered, bis(aqua)[μ-(terephthalato-κO)]copper(II), Cutp(OH2)2 (2), structured materials. 1 (C8H10CuO7) belongs to the orthorhombic P21212 space group [a = 6.3015(4) A, b = 6.8743(4) A, c = 22.9972(14) A, and Z = 4] and incorporates tp in a bridging bis-monodentate binding mode and Cu(II) in a tetragonally elongated octahedron. 2 (C8H10CuO6) which belongs to the orthorhombic Pmc21 space group [a = 10.7421(8) A, b = 7.2339(10) A, c = 5.7143(13) A, and Z = 2] incorporates tp in a mono-bidentate binding mode and Cu(II) in a distorted square pyramid. 1 and 2 exhibit axial X-band powder EPR spectra with g⊥ = 2.08, g∥ = 2.29 (1) and g⊥ = 2.07, g∥ = 2.29 (2) at 300 K. 1 obeys the Curie−Weiss law at high temperatures (θ = −7.2 K) and at low temperatures behaves as 1-D magnetic chains with an exchange-coupling const...

Observation of Ferromagnetic and Antiferromagnetic Coupling in 1-D and 2-D Extended Structures of Copper(II) Terephthalates.

To elucidate the mechanism of the reaction between V0(C6H6)2 and tetracyanoethylene (TCNE) that leads to the room-temperature magnet V[TCNE]]x·yCH2Cl2 (x ∼2; y ∼1/2), reactions between bis(arene)vanadium (arene = 1,3,5-trimethylbenzene, 1,3,5-tri-tert-butylbenzene) and its cations and TCNE and its anion were studied. The reaction of Vo(arene)2 with TCNE yields magnets with critical temperatures ranging from 28 to 400 K. Products from the reaction of [VI(arene)2]+ with [TCNE]•- were not magnets; however, reaction of [VI(arene)2]+ with [TCNE]•- in the presence of TCNE forms a magnetically ordered material. The reaction of V0(1,3,5-C6H3Me3)2 with 2 equiv of one-electron oxidant [FeIII(C5H5)2]+, and subsequently with [TCNE]•-, also leads to a magnetic material. The results of these investigations suggest that V0(arene)2 undergoes two one-electron oxidation reactions with TCNE to form sequentially [VI(arene)2]+ and “[VII(arene)2]2+”, the latter being the key intermediate that reacts with [TCNE]•- to produce th...

Laura Deakin

Papers

Observation of Ferromagnetic and Antiferromagnetic Coupling in 1-D and 2-D Extended Structures of Copper(II) Terephthalates.

Identification of [MII(Arene)2]2+ (M = V, Cr) as the Key Intermediate in the Formation of V[TCNE]x·ySolvent Magnets and Cr[TCNE]x·Solvent

Copper(II) carboxylate dimers and chains

Isotactic Poly(2-vinylpyridine), Coordination Polymers, and Magnetic Nanocomposites from Chromium Atoms